Method of preparing ureido grease-thickener concentrate and lubricating greases containing same



Fe 1 I T. TRAISE ETAL 2,925,387

METHOD OF PREPARING UREIDO GREASE-THICKENER CONCENTRATE AND LUBRICATING GREASES CONTAINING SAME il d July 21, 1958 2 Sheets-Shefl 0/L 1300mm TE 0/L-AMl/VE\ MIXER w UZ/wm:

SPRAY TOWER v Y J INVENTORS:

Thom/on R T raise F I Wilbur L. Hayne, Jr.

. Kemp R. Bunting ATTORNEY Feb. 16, 1960 T E ETAL 2,925,387

METHOD OF PREPARING UREIDO GREASE-THICKENER CONCENTRATE AND LUBRICATING GREASES CONTAINING SAME Filed July 21, 1958 2 Sheets-Sheet 2 I Fig. 2

m Wilbur L. Hay/re, Jr.

/ Kemp R. Bunting ATTORNEY preparing a;preforni'ed concent fict' of-ahydfoabietylfami' ar'ninerallubricatingoil w corporated in additionalmineral 'lubricatiii o l lubricating] grease composition-v; Other. ob ect METHOD OF PREPARING IUREIDO GREASE- THICKENER CONCENTRATE AND LUBRI-*-- CATING GREASES CONTAINING SAME Thornton Traise, Chicago Heights, 111., and Wilbur L.

Hayne, In, Hammond, and Kemp R. Bunting, East Chicago, Ind., assignors to Standard Oil Company, Chicago, 111. a corporation of Indiana Application July 21, 1958, Serial No. 150,015 :1 11 Claims. 01; 252-515 1 l This-invention relates to an improvement in thespreparation of a grease-thickener concentrate, and more particularly pertains to an improved method of preparing a preformed oil concentrate .of'the reaction product of a hydroabietyl amine and an organic polyisocyanate.

The co-pending application Serial No. 750,050, filed July 21-, 1958, by R. J'. Rosscup and Hubert I. Liehe, describes and claims as a new composition of matter the reaction product of a h-ydroabietyl amine, e,g. dehydro: abietyl amine with an organic polyisocyanate, e.g. bi? tolylene diisocyanate, and lubricant compositions, such he, d esired -l -arnounts ,tbxobt oil concentrate of the reaction product of a hydroabietyl amine and an organic polyisocyanate. Another -object of the invention is to provide a method of preparing a preformed concentrate of la'lubricatingoil and the reaction product of a hydroabietyl amine. and an organic polyisocyanat e'; Still another object of the present inyention is to provide an improved method for "theflpreparation of a preformed concentrated;grease thickenerfcap'able offb eing incorporated in alubricatingjoil' to form greasecornposition; Aifurther object of t e finve'ntiori herein described is to prov-ide'fian d 'rnetlio ubricat ng oil yeliicle in p A h e; lubricating oil} com-i osition orftliefllubricatingi grease ompositiom- The pr'i formed: productissuitablyprep ed i "concentration in a lubricatingoil;. .It is an object of the present improved, method of preparing'lia'ipreformed lubricating lllYellilOIl 'to provide an' lu r tin ice radicals selected from the group consisting of a dehydroabietyl radical, a dihydroabietyl radical, and tetrahydroabietyl radical and mixtures thereof and R is an alkylene radical or substituted alkylene radical of from 1 to about 30 carbonvatoms or an arylene radical or va substituted arylene radical. The radicals R, R and R" .can contain substituents such as, for example, alkyl, alkoxy, cyano, aryl, hydroxy, carboxy, halogen, nitro and other substituent group. The alkylene radical can be straight and/ or branched chain, and the arylene radicals can be mononuclear or polynuclear such as phenylene, bi-

v25 as lubricating oil and lubricating grease compositions, containing such reactionproducts. In'respect tojlubria, c'ating compositions,.-the reaction product of therhydr o abietyluamine and'ithe. organic, polyisocyanate ".cansbe 7 1 t 1 formed insitu in-- thelubricating-, oil: vehicle, leg. itheEhye drocarbon oil ;orZthe freaction prdduc ,an beapreform'ed l gandthen iincorp'orated"'i1i th 0 diisocyanate 1 biph eny 4.1.12, i qx sid qsgan phenylene, naphthylene, anthrylene and phenanthrylene radicals. The. terms alkylene and arylcne radicals as used therein includes substituted alkylene radicals and substituted arylcne radicals.

The general structural formula of the hydroabietyl radicals are:

HaC

Examp esot liydroabietyl amine's i.e aliphatic amines attached tqaan"alicyclic structure, which'c'a'n be used ation of I thejabo'e de'ls cribed uieidocomponnds the prep lfi lli tc-diphenylmethan Patentedli'ebi 7' -T-he following is illustrative of the apparent reaction which takes place:

As disclosed in: the iRosscup et al. application, supra, lubricating grease; compositions are reipdilyiprepared by forming the hydrpabietyl amine-organic 'pclyisocyanate thickener in situ in- 'the lubricating oil vehicle. In addition to preparing such thickenersjlingsitu, it is desirable to form a thickener concentrate which can be mixed with additioual quantities of the lubrf 'ng. oil vehicle to produce"lubricating grease compositi'o" of the desired consistency. a

Substantially one hundred percent of the subject ureido compound (Formula, I, supray hard, white powder is readily prepared by reacting the ,hQydroabie'tyl amine and hers, provided with a suitable spray -nozzle attached to I the bottom thereof, and discharging. the mixture through said-sprayanozzlein the form of droplets into a spray tower-of:suitable-height before precipitation of the reaction productoccurs. As the droplets of the reaction mixture fall through thespray tower precipitation of the product occurs, fol-lovv'ed by the crystallization thereof. When: the: reaction product 'reaches the bottom: of. l the spraytower in the, form 'of;a relatively hard granular '7 solid; -it -is 'caught:or collected -=in' spans of suitable size.

the organic polyisocyanate in a volatile solvent, and

subsequently removing the; solvent by suitable means, e.g. under vacuum. 'The pureprqductso attained is diincult to incorporate in a,,lub'ricating oil vehicle to form an effective lubricating grease.

When solutionshfthe hydroabietyl amine and the is very rapid, and, in general, the rate of formation of th uteid ,mm qu i gr a tha the a of p on "atlthe' beginning] pf the reaction. As a result, nt e o .th tn s t s v p o nc ea e i t are itbe e es mor iifi sm n l j iiten ive mixmgrwhi h h a e y to iqt q ft layera q; s g fi e y talli ifi e oichioniet icallycona inef theitwo reactants without "h v isl wvc ed n a cor an e th the r s I The "collected granular 'solidj thickener} received in the collecting pan atlaet'eniperature of fromjabou't 150 F: totabout .2S0":?F.,' is removed from thes ray-tower and j allowedlo cool' togarribientroomtemperature. EThe'rIuBricatingXOiI. employed in the preparation of the herein described thickenerlis preferably a petroleum lubricatin'gf oil .of- 'theidesired :lviscosity; suitableoils .are solgent; extracted :01: otherwise. refined SAE l 0 f and w20i-base petroleum' dilsh :HoWevensdpending upon: the: intended uselzof thezrfinisheddubricating grease, other oils inzthe lubricating oil; viscosity range can the 2used,.- such' as,':for example silicone gpolymer oils, synthetic hydrocarbon I lubricating oils, and other synthetic lubricating oils such as polyalkylene glycols and their derivatives, high molecular weight esters of dicarboxylic acids, Jpolyfiuoro aderivatives of: organic compounds such as the trifluorovinyl chloride polymers known-as Fluorolube (madew;by

V Hooker'Chernica1 Company) and the-trifluorochlorob antially'instantaneously removing. the reaction soluprecipitation" and crystallization, jaJpale yellow granular concentrated thickener canbe obtained which'is readily i ethylene polymers, knownas Kel-F40 (made by The M,--W. ;,Kel1ogg Company), etc.

The present invention will be clearly understood from the following specific examples which is given by; way of illustration o ly and isnot to;-be construed as alirnitation f the inven ion- V Referrin'gto Figure :1," a' solutionpof about 25% {hitolylene diisocyanate'in'a solvent extracted SAE 10 base mineral oil is prepared in tank 11,; provided witha stirrer 1 2, lby heating ,themixture oiland isocyanate ata temperature; of-200 F. with continuousstir-ring, and a solu tion ofabout 75%-of Rosin 'Arnine D, supra, a solvent extracted SAE 10 tbase nineral oil is prepared in tank 13 provided with a stirrer '14 at al out,70: t?-() F. with continuous stirring. The oil-isocyanate solution from-tank I 1 and the oil-amine-s'olution from tank' .13

" are-pu pe thI9u sra d 6 p ps a f lls,

tainilig a -80% solution of;the"hydroabietyliamine in v a imbi-igtingoil at a temperature 'of from aboutiq tl" F. without-1100 pr'efe'rably' about 90' "*F., mt ago-30% of -the"organic polyis'ocyanate in a' 'lii aFtemperatnie pr from-about -1so -=F, 'i b ing the two solutions into suitable-variableinixing ehainlines 1 7a and 18a respectivelytothe.variable volume mixer19 (hereinafter described in detail) located at the top of a spray tower 20. Pumps l7 and 18, which are suitable gear pumps, are geared to operate at the same rate and therefore deliver the same'volumes of the solutionsfrorn tanks 11 and 13 to the mixer 19. The volume of the variable mixer19 is eadjustedto the.:point where ware arm the entering, reactants are action product occurs; f

iflhe loil-isocyanate solution entering the "inixerf19, at) ajternperature' of 160-190 F. and the oil-amine solution f entering the mixer 19 atatempeiature of YO-100 are contacted with each other therein and reaction initi ated immediately; The reacting mixture'moves rapidly through the mixer 19 and is"sprayed into spray. tower/20 through spray nozzle v21,loca ted in the'bottom of the; mixing chamber 19 and projecting into the top of spray,

tower 20. As the admixed solution is discharged from the spray nozzle 21 in the form of droplets, precipita tion of'the reaction product as re'lativelyjhard granular solids occurs as it falls through the spray tower 20; The

reaction product is, collected in suitablercontainers 22,

e.g relatively shallow steel'pans at the bottom of the spray tower 20, which are removed from the spray tower as they become filled. The temperature at the interior of a batch ofthe thickener concentrate immediately after removal from the spray tower is in the range of from about 150 F.-O F. The product'after cooling to t ambient room temperature is in the form of loose agglomerates which are readily crumbled ,to give a pale yellow granular solid having the appearance: of light yellow sugar.

The details of the mixer 19,. fabricated of a suitable metal, preferably of brass or bronze, are" shown in Figure 2. Referring to Figure 2, mixer 19 consists of a body. portion 23 and a chamber 24 in communication with line 17a through inlet 25, and in communicationwith line 18a by means of pipe or tube 26 having a sealed. end 27 and aplurality of holes28 spirally "spaced inf the, portion thereof extending from withinl-the'chamber l 24, The tube .26 extendsthifough mixing chamber 24* andis concentric with the'nozzle, mount 29, hereinafter-1 described. The open end of chamber,24 isthreadedfto receive threaded nozzle mount 29*which ofisuflicien't is @variediand'controlled by the distanceetowhichjthe threaded'nozzle mount 29' is threaded into the chamber 24. Asthernozzle mount 29 is threaded farther into the chamber 24 1ess mixing of the solutions occur in chamber 24 and more mixing takes place in the annular space 31 between the tube 26 and the nozzle mount 29. The

distance in which the nozzle mount 29 extendsinto" chamber 24 can be so adjusted that the two oil solutions are admixed and expelled-through the'nozzle 21 into the spray tower 20 before any substantial precipita tion of the reaction product occurs. 7

Using a 20% to solutionof bitolylene diisocyanate in a mineral-oil and a 70% to 80% solution of a hydroabietyl amine such as 'Rosin Amine D in a mineral oil, will yield a thickener concentraterha'vin'g a typical analysis of about 44-47% thickener,-1 to 5% free amine and (iii-1.5% undetermined. By varying the quantities ofr the hydroabietyl amine and of the organic polyisocyanateconcentrates containing 25-60% of the thickener (Formula I, supra) can be prepared by the above described spray technic.

Although in the foregoing, specific examples, illustra- I tive of our invention, we have used Ebii0lyl6l16-dllS0 cyanate other aryl or alkyl polyisocyanates such as above disclosed, can be used. I V a Lubricating grease compositions oflany desired consistency, i.e. thickener concentration, can be obtained by incorporating, by a variety of methods, the desired amount of the thickener concentrate in asuitable lubricating oil. A suitable method comprises combining in a'grease kettle 1620 parts of the thickener concentrate V v qu t y ed: nd, 7 charged from themixer before precipitation ofjthe grease composition containing about 10% of th'ethickener (Formula 'I,- supra). The resultant fluid. mixture is heated to about 390-1400 F., held at said temperature :for

, about 35+40' minutes and then cooled to about 200 10 andpassed through a' colloid 7 mill.

prepared from, preformed thickener concentrates, ob:

tainedby the method of -the 'present invention are comparable, as shown by the data in Table I, The 5;thickener used was the reaction product of bitolylene diisocyanate and Rosin Amine D, supra.

Table I Preformed Formed I r a In Situ- Percent-Thickener 8 7 Mechanical Stability, Percent Chan -5 r 5 25 Leakage Assistance, Percent Loss 2, 5 2.0 Water Resistance Excellent Excellent Drop Point, F -'480. 1 0

The feature of the above greases include mechanical I 0-;stability, leakage, water resistance, and a high drop point. a

claims arewby weight, unlessptherwise stated,

' and spirit of th appe d d c aims 1'; -We laimzz, Y

having the general formula oil, (2) rapidly mixing together equal proportions of said oil solutions for a time'sufiicient'to initiate reaction between said amine and said polyisocyanate, but insuf- 0 fi'cient tocause precipitation of any reaction product, (3) spraying, in the form of droplets, said admixed oil solutions of said reactants into the top' of a spray tower t 'before.-precipitation of the reaction product occurs, (4) permitting said droplets to descend in the spray towertfor a time sufiicient for said droplets to form a solid granular precipitate, and" (5) collecting said 'soli anular precipitate. ,e a r g 2.'The methodof claim 1 in which the organic polyisocyanate is an aryl polyisocyanate;

3. The method'of claim l'in which the organic polyisocyanate is bitolylene diisocyanate. r 4. The method ofclaim 1 in which the organic polyisocyanate is an alkyl polyisocyanate;

5. The method of claim 1 in which the lubricating oil' is a petroleumlubricating'oil.

(approximately 50% I thickener) and- 10-18 parts of a r solvehtextfactd sAE 10 base?m neralqenandnmn '1 v tot for'rn -a heavy baselaf-The heavybase-is therii he'ated'l 16 about zoo nr'ana graded-with 65-70- part'sfof'a, V

solvent "extractedSAE 40 base mineral oil to give a fluid Greases prepared by'formin'g the thickener in situ and Percentages and parts given herein and in the appended 2 Although the present invention has been described with I ;:reference to specific embodiments'ithereof,=the. invention; 5 a. isnot limited thereto, but includes within its scope such I modifications and variations as come within thescope ,;,The method a concentrate of lubrifj eating oilcontaining at least 25% of a ureido ,cqmpound;

6. Theirneth'od ,of preparing a concentrate of a lubri-f' at least oneureido compound havin'gth'e general formula wherein R" and R" are hydroabietylradicals selectedfrom the group'consisting of a dehydroabietylradical, a dihydroabietyl radical, atetrahydroabietyl radical and mixtures thereof, and R' an arylene radical, comprising thestepstl) forming separate solutions of about 70% to about 80% of a hydroabietyl amine in a lubricating. oil'and of about 20% to about 30% of an aryl poly-- isocyanate in -a lubricating oil, (2) rapidly mixing together equal proportions ofsaid'oil solution of said aryl polyisocyanate at a temperature of from about 150 F. to about 250 F., and said oil solution of said amine at a temperature of from about 70 F. to about 100 F.

for a time sufliqient, to, initiate reaction between said amine and said ,polyisocyanate, but insuflicient to cause precipitation of any reaction product, (3) spraying, in

the--form--ofdroplets, said admixed oil solutions -of--said reactants at a temperatureoffrom about 150?" Fr to:

about 250 'F., into the top of a spray:towerx before precipitation of the-reactionhproduct occurs,:2(4) ;per-

lar precipitate, (5) collecting saidsolid granular precipitate; and cooling to embient room-temperature;

7'. The method-of claim -6 in which the'hydroabietyl amine is a mixture consisting essentially of about 60%- dehydroabietyl amine,- about 30% dihydroabietyl-amine and about-l0%' tetr'ahydroabietyl amine.

'8-.; The methodof claim-'6 in which the arylfpolyisocyanate is bitolylene diisocyanate. a

9; The method ofclaim-fi-in which the lubricating; oil is-a-hydrocarbon lubricating oil;

10. The method of preparing'a' lubricating greasecomprising a lubricating oil thickened with a thickener concentrate comprising a lubricating oil containing at least '25 mitting said droplets to descend in the-spray tower for a time suflicient for said droplets to form a solid granu- 25%" of aureido--compoundhaving-the general formula wherein R andgzR'. arehydroabietyl radicals selected from the, group consisting,

mixturesv thereof, and R' is an ,organicradical selected from the group consistingof an alkylene" radical ofvfrom 1 to about 30 carbon atoms, and anarylene radicaband.

prepared by the method of claiin, 1, comprisingtmixing said thickener'concentrate, with a small amountvof a, lubricating oil, heating said mixture to a temperature of 200 F. while stirring, addingiadditional lubricating oil in. an amount sufiicient .to obtain the desired lubricating grease consistency, raising the temperature of the mix-1.

ture to about 390-400. F., andmaintain the .said tern-l perature for about 30-40 minutes, cooling the mixture to atemperature of about 200 F., and passing the mix,

ture through acolloid mill.

11. The method of preparinga lubricating grease comprising alubricatingoil thickeneclwith a thickener concentrate comprising; a lubricating oil containing about 45T50% of'a ureido compound having the general form-v I ula non HOE Ill! l-ll in which R andVR'f are hydroabietyl radicals selected from the group consisting of a dehydroabietyl radical, a dihydroabietyl radical, a tetrahydroabietyl radical. and

mixturesthereof, and R is a bitolylene radical, and preparedby the ,method of claim 1, comprising mixing said ,tliiclgenerconeentrate, with a small, amount of a lubricat ingzoil, heatingsaid mixture to a temperature of-200 a i "Referen cesCitedin the file of this patent UNITED STATES PATENTS 1,772,687 Spensley July 30, 1929,- 1,937,463 Nill Nov.- 28, .1933 2,383,906. Zimmeret a1 Aug. 28,1945

2,710,841. Swakon et al. June '14, 1955 A of a dehydrtiabietyl radical,v a dihydroabietyl radical, a "tetrahydroabie'tyl,tadicalfandi UNITED STATESPATENT OFFICE Y Certificate of Correction Patent No. 2,925,387

Thornton P. Traise et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

In the grant, line 1, and in the heading to the printed specification, line 5, name of first inventor, for Thornton Traise, each occurrence, read Thornton P. Traise; in the heading to the drawings, sheets 1 and 2, line 1, for T. Traise et a1. read -T. P. Traise et al.; column 2, lines 25 to 30, Formula III, the lower right-hand portion should appear as shown below instead of as in the patent:

H H column 7, line 7, for wherein R' read wherein R.

Signed and sealed this 2nd day of August 1960,,

Attest KARL H. AXLINE, ROBERT c. WATSON, Attesting Ofiicer, Uomnnissioner of Patents.

. February 16, 1960 

1. THE METHOD OF PREPARING A CONCENTRATE OF A LUBRICATING OIL CONTAINING AT LEAST 25% OF A UREIDO COMPOUND HAVING THE GENERAL FORMULA 